Emulsion copolymerization of styrene with monomeric emulsifiers

Monomeric emulsifiers with different copolymerization reactivities were used as stabilizers in emulsion polymerization of styrene initiated by 2,2′ azobisisobutyronitrile (AIBN). A significant change in emulsifier function was observed between equal micellar concentrations of surface-active sodium sulfopropyl alkyl maleates and the corresponding sodium sulfopropyl dodecyl fumarate. In the presence of less reactive maleates, copolymerization mainly occurs in the interface of the monomer swollen particles, while copolymerization with the fumarate in the first period of emulsion polymerization leads to polyelectrolyte formation in the water phase.     

The Silicides M4Si4 with M = Na,K, Rb,Cs, and Ba2Si4 – NMR Spectroscopy and Quantum Mechanical Calculations

The Zintl phases M₄Si₄ with M = Na, K, Rb, Cs, and Ba₂Si₄ feature a common structural unit, the Si₄^4– anion. The coordination of the anions by the cations varies significantly. This allows a systematic investigation of the bonding situation of the anions by ²⁹Si NMR spectroscopy. The compounds were characterized by powder X‐ray diffraction, differential thermal analysis, magnetic susceptibility measurements, ²³Na, ²⁹Si, ⁸⁷Rb, ¹³³Cs NMR spectroscopy, and quantum mechanical calculation of the NMR coupling parameter. The chemical bonding was investigated by quantum mechanical calculations of the electron localizability indicator (ELI). Synthesis of the compounds results for all of them in single phase material. A systematic increase of the isotropic ²⁹Si NMR signal shift with increasing atomic number of the cations is observed by NMR experiments and quantum mechanical calculation of the NMR coupling parameter. The agreement of experimental and theoretical results is very good allowing an unambiguous assignment of the NMR signals to the atomic sites. Quantum mechanical modelling of the NMR shift parameter indicates a dominant influence of the cations on the isotropic ²⁹Si NMR signal shift. In contrast to this a negligible influence of the geometry of the anions on the NMR signal shift is obtained by these model calculations. The origin of the systematic variation of the isotropic NMR signal shift is not yet clear although an influence of the charge transfer estimated by calculation using the QTAIM approach is indicated.     

Emulsion polymerization in the presence of polymerizable emulsifiers and surface active initiators

A survey is given of recent developments in emulsion polymerization regarding improved auxiliary materials, e.g. vinyl tensides and surface active initiators. Results of the emulsion polymerization of styrene are presented with 3-(alkyloxycarbonyl-acryloyloxy)propanesulfonates ( 2 ) as polymerizable emulsifiers and with surface active azo initiators. The results show, that the content of water soluble surface active compounds in the latexes can be reduced. Investigations of the molecular weight of the polymers show the great importance of the initiator-emulsifier system. Azo initiators leading to higher molecular weights than persulfate. Under the same conditions the highest molecular weights were obtained with a surface active azo initiator.     

Computer-Driven Development of Ylide Functionalized Phosphines for Palladium-Catalyzed Hiyama Couplings

Palladium-catalyzed couplings of silicon enolates with aryl electrophiles are of great synthetic utility, but often limited to expensive bromide substrates. A comparative experimental study confirmed that none of the established ligand systems allows to couple inexpensive aryl chlorides with α-trimethylsilyl alkylnitriles. In contrast, ylide functionalized phosphines (YPhos) led to encouraging results. A statistical model was developed that correlates the reaction yields with ligand features. It was employed to predict catalyst structures with superior performance. With this cheminformatics approach, YPhos ligands were tailored specifically to the demands of Hiyama couplings. The newly synthesized ligands displayed record-setting activities, enabling the elusive coupling of aryl chlorides with α-trimethylsilyl alkyl nitriles. The preparative utility of the catalyst system was demonstrated by the synthesis of pharmaceutically meaningful α-aryl alkylnitriles, α-arylcarbonyls and biaryls.     

Manganese(I) Catalyzed ortho C−H Allylation of Benzoic Acids

The 3d-metal catalyst Mn(CO)₅Br was found to efficiently promote ortho C−H allylations of arenecarboxylates in the presence of neocuproine as the ligand. Despite the simplicity of directing group and catalyst system, the selectivity goes well beyond the state-of-the-art in that mono-allylated products are obtained exclusively with high selectivities for the least hindered ortho-position. The directing group can optionally be removed by in situ decarboxylation, opening up a regioselective entry to allyl arenes. The preparative utility of the process and its othogonality to other approaches was demonstrated by 44 products with otherwise hard-to-access substitution patterns, including 3-bromo-allylbenzene, 3-allylbenzofuran, or 5-allyl-2-methylnitrobenzene.     

Optimization of resolution in micellar electrokinetic chromatography

A comparison of separations conducted in sodium dodecyl sulfate (SDS) and SDS modified with Brij 35 indicates that selectivity, in Micellar Electrokinetic Chromatography (MEKC), is governed by the composition of the micellar phase. Beyond selectivity optimization, resolution may be improved by increasing efficiency or decreasing electroosmotic flow. Of these approaches, increasing capillary length (to improve efficiency) should be a more time effective means of improving separation.